一元硝酸酯热解反应的理论研究

Theoretical Study on Pyrolysis of Mononitrate Esters

运用SCF－AM1－MO方法，计算研究了十个一元硝酸酯的热解反应，揭示了烷基取代对反应过程的影响．UHF计算O－NO2键均裂产生RCH2O·和·NO2两个自由基的反应活化能较低，是硝酸酯热解的主要途径;RHF计算α-H转移环消除产生RCHO和HONO的反应具有较高活化能，且α-C上含两个以上取代基时不发生该反应．还探索性地进行了C－O键断裂的UHF和RHF计算．.

The pyrolysis reactions of ten mononitrate esters have been studied by using SCFAM1-MO method. The effect of alkyl substitution on the mechanism of reactions is discussed.UHF calculations show that homolysis of O-NO2 bond into two radicals RCH2O·and·NO2 has lower activation energy and is the main way of pyrolysis. However, RHF calculations indicate that breaking of O-NO2 is a α-H transition elimination reaction with products RCHO and HONO and quite high activation energy, and can't occur when there are more than two alkyl substitution groups on α-C. The cleavage of C-O bond has also been studied by UHF and RHF calculations.